Aminoketones



United tates Patent C l 2,969,359 AMINQKETONES Peter L. de Benneville, Philadelphia, Pa., assignor 'to Robin &Haas Company, Philadelphia, Pa, a corporatioh of Delaware a Nama Filed Mar. 24, 1958, s No. page; 8 Claims. crew-247.7

This invention concerns specificaminoketones as new compositions of matter.

The compounds of this invention may be represented by the following formulas:

in which R and'R taken individually, represent alkyl groups of not over'four carbon atoms and, tahencollectively, represent a divalent saturated aliphaticchaln of four to five atoms which jointly with the amino nitrogenforms 'affiveto s'iX- mernbered heterocyclictuouosymbol R represents an allryl group ofnot over seventeen carbon atoms, an allre'nyl group ofthree t seventeen carbon atoms, or an"-aryl or-substitu ted 'aryl ofsix" to about twentytarbon atoms. Alkyl in this sense is to be cemeteri including cycloallryl. Actually", may also be alkynyl group of threeto seventeen carbon atoms provided that neither of the carbon "atoms connected by the triple bond 'bears'a hydrogen atom. However, the alk'yl and'allreiiyl representations o fRg are Preferred. i i e symbol R stands for an aryl or substituted aryl group of six to about twenty carbon atoms."Typica1 groups thatRpmafreprsent include phefiyl, chlorophe'r'tyl, diehlorophenyl, trichlorophenyl, dibro-mophenyl, 1 15/1, "Xylyl," trimethylphenyl; 'thylphenyl, d'ithylphenyl, triethylphenyl, 'metliylethylphefiyl, butylphenyl, T tributyl phenyr,=uuen 1pneay1, piityl'phenyl, dipe'ntylphe'nyl; iiiheirylphenyl', h'exe'nylpheiiyl', butylhexylphenyl; diheptylphenyl, octylphen'yl, ooter'aylph'enyl; 'nonylphenyl,-"*ethylnonylphen'yl, decylphenyl, do'decylphenyl, "dodecenylphenyl, inethyldodecenylphenyl; tetradecylphenyl, butoxyphnyl, octox pnenyt, decoXyphenyl, butoxybutylph'enyl, octoxyethylphenyl, naphthyl, methylnaphthyl, 'ethyl'naphthyl, 'butylnaphthyl, butenylnaphthyl, octylnaphthyl, decylnaphthyl, de'ceriylnaphthyL' chloronaphthyl, dichloron aphthyl, and brom'ona'phthyll Typical 'groups' that R may represent, in addition to those listed as typical of Rg, include methyl, ethyl, propyl, butyl, "cyclopentyl; cycloheiryl,"heptyl, "octyl, decyl, dodecyl, tetradecyl; heptadecyl, allyl,*butenyl', hexenyl, octen'yl', nonenyl,decenylyclodecenyl, and heptenyl. R and R taken singly, may represent-alkyl' groups of no'm'ore than four carbon atoms, that is,'methyl, ethyl, 'propyl," or butyl groups, in which case R and R may be the same or difierent'.-'R' and'R taken together and in conjunction with the amino'nitrogen, may stand for amorpholino, thiamorpholino, pyrrolidinyhor piperidino roup. a t ese up ha ing one q fm ow alkyl substituents, such as methyl and ethyl groups.

2,969,359 Patented Jan. 24, 1961 The alkyl groups of R R R and R and the alkenyl groups of R and R may be straight or branched chains in any of the known spatial Configurations. The 'substituents on the aryl groups, in R and R may be at any of 'the possible ring positions. While, of course, some spatial configurations and ring positions arepreferred over others, allpossible configurations and positions are satisfactory for'the present purposes. V

The compounds 'of'this' invention of the type Formula II are prepared by reacting with CH COR in equimolecular proportions and then with CH COR in'equimolecular proportions; To obtain a Formula 11 compound, there is reacted on a one for two molar basis R1 CH3 on, ciao R2 Ha with CH COR The reactants of this invention,

Rt I fill;

NCHzCCHO t; Hi

R.\ on; Ma an are known or can be readily made by the reaction of the appropriate secondary amine hydrochloride with formaldehyde and isobutyraldehyde according to known methods.

The present compounds whether of the type of Formula I or 'II' are prepared by bringing together at a reacting temperature the"selectedreactants;depending on the formulafltype productde'sired, as discussed-heretofore. Temperatures in the range ofabout 0C. to the reflux temperature of the reaction mixture may be used. Generally, temperatures between about 20 to C. are employed, with 25 to 80 C. preferred. i V

' A strongly'basic catalyst is required for the consummation of the instant reaction. Suitable for this purpose are alkali metals, such as sodium, potassium, or lithiumlalkali metallower' alkoxides, such as s'o'dium-methoxide, potassium ethoxide, lithium methoxide, sodium ise' 'm poxide, quaternary ammonium bases, such as trimethyl benzylammonium hydroxide, and thelike.

An insert volatile organic solvent is preferably employed such as benzene, toluene, ethanol, isopropanol, tert-butanol, ethyl ether, isopropyl ether, dioxane'gand the like. At the conclusion of the reaction, the solvent may be removed, when desired, :b'y'distillation, preferably under reduced pressure, or by evaporation, such as on a steam bath.

The time of reaction is not especially critical. Reaction times in the range of two to ten hours have been found satisfactory. Shorter or longer times may be employed as desired. Generally, of course, the shorter reaction times sometimes have a tendency to reduce the yield of product and the longer reaction times tend to maximize that result. This will all be clear to one skilled in the art from the teachings of this invention.

If the product of the type of Formula I is desired, there is reacted the formula with CH COR on an equimolecular basis and then with CH COR on an equimolecular basis. By carefully employing equimolecular amounts of reactants, a product of high purity is obtained. If the Formula I product is a liquid, which is usually the case, it may be isolated from the reaction mixture by first adding an excess of a strong mineral acid, such as hydrochloric, sulfuric, or phosphoric, in any convenient concentrations, such as aqueous 5 to solutions. The acid destroys the catalyst and at the same time forms an acid salt of the amine product. If small amounts of extraneous substances are present in the acidulated mixture, an extraction may be performed using chloroform, benzene, ethyl ether, or the like. The mixture is made basic to free the amine product and then the product is extracted with the same solvents as mentioned before or with similar ones. The solvent is removed, preferably on a steam bath, leaving the product. In some instances, paniculan 1y where the lower molecular weight products are concerned, it may be advantageous to strip 05 the solvent and distill the product, preferably at reduced pressure. Distillation of the higher molecular weight products is not recommended because some of them have a tendency to decompose at the higher temperatures. If the Formula II product is a solid, it may be filtered off, washed and then recrystallized from a suitablesolvent, including lower alkanols, such as ethanol, isopropanol, or the like, and dried, such as over anhydrous sodium sulfate or on yellow to tan in color.

To make a product of the type of Formula II, there are reacted a steam bath. The Formula 11 products are generally and CH COR in a one-to-two molecular ratio. These products are generally solids that may be isolated in a manner similar to the solid products of Formula I.

Whether a Formula I or II type product is being prepared, the yields consistently exceed 90% and frequent: ly are substantially quantitative. The compounds of this invention are valuable as highly selective plant growth regulators. As indicated by the standard Lanolin Ring Method, in which a lanolin, paste containing 1% of a compound of this invention is employed, and Coated Sand Method, in which 32 mg. of a present compound is used to coat 20 g. of quartz sand in which the test seeds are planted, the present compounds-are excellent herbicides for dicotyledonous plants while not substantially interfering with the growth of monocotyledonous plants. In many instances the present compounds com-i pletely inhibit dicotyledonous plants and in all other cases cause considerable damage on the dicotyledonous plant life whose inhibition is desired. While all of the present compounds are valuable as selective herbicides,

a particularly outstanding performance is observed with on, CH3

uomocmorncoofiunz C a Hs This unusual selctive herbicidal activity permits the use of the present compounds in many situations not available to many known commercial preparations.

The compounds of this invention may be used as herbicides in any of the usual ways of distribution. They may be employed in dusts, wettable powders, self-dispersible concentrates, solutions, or suspensions. Compositions suitable as dusts are prepared from a compound or compounds of the present invention dispersed in a solid carrier such as talc, clays, pyrophillite, diatomaceous earths, or mixtures thereof by grinding the components together or by depositing the subject compound on the solid carrier from a volatile solvent and evaporating the solvent, if desired. The subject compound is preferably present in the range of one-half to which is the most eifective herbicidal range, when used in a dusting composition. A small amount of a suitable wetting and/or sticking agent may be employed, if desired, such as a condensate of polyglycerol and a long chain fatty acid, with or without reaction with phthalic anhydride.

Compositions suitable as wettable powders are prepared from a compound or compounds of the instant invention, usually present in the range of about 25 to mixed with about I to 5% of a suitable wetting agent such as a water-soluble, surface-active alkylphenoxypolyethoxyethanol, a condensate of ethylene oxide and oleic acid or tall oil fatty acid or rosin acid, a condensate of ethylene oxide and long-chained mercaptans, sodium dodecyl sulfate, or sodium alkylbenzenesulfm mates and about one-half to 3% of a suitable dispersing agent, such as a soluble salt of a copolymer of maleic anhydride and an unsaturated hydrocarbon such as styrene or octene, a formaldehyde-condensed naphthalene sulfonate, or a lignin sulfonate. This mixture is then formulated with a sufficient amount of a solid carrier, of the kinds set forth above, to make Such a wettable powder may be suspended in an aqueous medium and applied in a spray. The active compound is preferably present in the final formulation in the range of about 0.02 to 0.5%, which is the most efliective-herbicidal range.

Compositions suitable as self-emulsifiable or self-dispersible concentrates are prepared from a compound or compounds of this invention, usually present in a range of about 25 to 98%, mixed with about 1 to 25% of a suitable emulsifying agent, such as a water-soluble, surface-active addition product of ethylene oxide and methylene bisdiamylphenol, octylphenoxypolyethoxyethanol, polyglycerol toleic acid condensates, or sorbitan laurate or mixtures thereof. If desired, a suitable dispersing agent, such as a soluble salt of a copolymer of maleic anhydride and an unsaturated hydrocarbon such as styrene or nonene, a formaldehyde-condensed naphthalene sulfonate, or a lignin sulfonate, may be employed in an amount of about one-half to 3%. Also, if desired, an inert organic solvent for the instant compound, the wetting agent, and the emulsifying agent, such as an aromatic naphtha, xylene, solvent esters, etc., may be employed usually in the amount of about 3 to 70%. There may similarly be used water-miscible solvent such as acetone or methyl ethyl ketone or dioxane. This concentrate is then added to a suitable medium, such as water, where it becomes emulsified or suspended without the necessity of the inclusion of additional agents. The instant compound is preferably present in the final formulation in the range of about 0.01 to 0.5% which is the most practical herbicidal range. i

For greatest ease or application and maximum distribution effects, it is desirable that the present compounds be used in an aqueous spray. Anotherfrnethod of preparing a spray includesadding thefdesiredamount of one ofthe present compounds, taken upin about .5 of a suitable solvent such. as acetone, to water containing about 2% of a suitable wetting agent such as those previously listed. Suificient compound. should be. added to assure the .applicationof about one-eighthto, one pound of the compound in a sufiicient quantity byaqueous solutionfor application to one acre. Conveniently, spray, isapplied to about 40 gallons per acre, so. the proper amount ofcompound to be added can beeasily calculated.

Specific formulations that have been. found to be highly satisfactory include the following, in which parts by weight are shown.

DUST- 22.79 parts-clays 2.21 parts-a compound of this invention,

WETTABLE POWDER 84.3 parts-a compound of this invention,

2 parts-water-soluble, surface-active alkylphenoxypolyethoxyethanol,

1 partsoluble salt of a copolymer of maleic anhydride and octene,

12.7 parts-clays.

This wettable powder, in the amount of 1.33 pounds, is added to 40 gallons of water for a one-acre application.

CONCENTRATE 97 parts-a compound of this invention,

2 parts-water-soluble, surface-active alkylphenoxypolyethoxyethanol,

1 part-soluble salt of a copolymer of maleic anhydride and octene.

This concentrate, in the amount of 1.16 pounds, is then added to 40 gallons of water for a one-acre application.

The compounds of this invention are useful herbicides when employed in either a pre-emergence or post-emergence application, as desired. The post-emergence ap plication produces somewhat better control and is, therefore, the recommended procedure.

The compounds of this invention as well as their method of preparation may be more fully understood from the following examples which are olfered by way of illustration and not by way of limitation and in which parts by weight are used throughout.

Example I There are introduced into a reaction vessel 1.5 parts of metallic sodium in 18 parts of anhydrous ethanol and then 60 parts of methyl octenyl ketone. There is added dropwise 50 parts of u-(dirnethylaminornethyl) isobutyraldehyde. The mixture is heated to reflux for six hours and then added, with cooling, to 50 parts of aqueous 37% hydrochloric acid in 75 parts of water. The resulting mixture is extracted with ether to remove any acid insoluble material. To the aqueous solution, there is added 55 parts of an aqueous 50% solution of sodium hydroxide. The product is extracted with ether and the ether extract is dried over anhydrous sodium sulfonate and the ether removed on a steam bath. To this there is added 200 parts of absolute ethanol in which there is dissolved 5 parts of sodium. To the resulting mixture, there is introduced 17 parts of methyl naphthyl ketone. The mixture is allowedto stand at room temperature (22 to 28 C.) for five days and is then neutralized with an aqueous hydrochloric acid solution and filtered to remove precipitated salts. The filtrate is freed of solvent by evaporation leaving a dark oily product which gives an analysis for the compound havingtheformula OH; on, CHzCOCwH'I.

on on, f 39 CH .3 .99 11 In like manner, from u-(dimethylaminomethyl)isobutyraldehyde, methyl bute nyl ketone, andmethyl butenylphenyl ketone, there is made the product having the formula OH; on; 011 00031 NCHi OH\ a Q tPQQC Z Example 2..

To a solution of 6.9 parts of sodium in 75 parts of absolute ethanol, there are added 40 parts of acetophenone and 30 parts of a-(dimethylaminomethyl)isobutyraldehyde. The mixture is held at 22 to 26 C. for ten days and then filtered. There is obtained a crystalline product which melts at l0ll02.5 C. and is identified as 1,1 di(benzoylmethyl) 2-(dimethylarninoethyl)-2- methylpropane. The product contains 3.82% nitrogen, 78.9% carbon, and 8.36% hydrogen.

In a like way, from methyl octylphenyl ketone and a-(rnorpholinomethyl)isobutyraldehyde, there is prepared 1,1 di(octylbenzoylmethyl)-2-(morpholinomethyl)-2-methylpropane in the presence of trimethylbenzylammonium hydroxide, using reacting temperatures of 48 to 55 C. for 16 hours.

This case is a continuation-in-part of United States Serial No. 561,340, filed January 25, 1956, now abancloned.

I claim:

1. As a composition of matter, a compound from the group consisting of R CH3 CHQO OR;

NCHzCCH Ra CH; GHROOR and R1 CH3 NCHzCEKCHzC 0 R in which R, and R taken singly represent alkyl groups of one to four carbon atoms and taken collectively with the amino nitrogen atom to which they are attached form a heterocyclic group selected from the class consisting of morpholino, thiamorpholino, piperidino and pyrrolidinyl, R is a member from the class consisting of alkyl groups of one to seventeen carbon atoms, alkenyl groups of three to seventeen carbon atoms, and aryl and substituted aryl groups of six to twenty carbon atoms, and R is a member of the group consisting of aryl and substituted aryl groups of six to twenty carbon atoms, said substituted aryl groups being free from in R1\ CH3 CH O R NCHtC CH CH3 CH2C 0 R in which R and R are alkyl groups of one to four carbon atoms, R is an alkyl group of one to seventeen carbon atoms and R is a phenyl group.

3. As a new composition of matter, the compound having the formula NCHzCH(CH2COR1) R! H:

in which R and R are alkyl groups of one to four carbon atoms and R is a phenyl group.

4. As a new composition of matter, l-(dimethylamino) 2,2 dimethyl 3-(naphthylcarbonylmethyl)-3- (octenylcarbonylmethyl) -propane.

5. As a new composition of matter, 1,1-di(benzoylmethyl) -2- dimethylarninoethyl) -2-methylpropane.

6. As a new composition of matter, 1,l-di(octylbenzoylm ethyl -2- (morpholinomethyl) -2-methylpropaue.

7. As a new composition of matter, I,1-di(p-butylbenzoylmethyl) -2,2-climethyl-3-pyrrolidinylpropane.

8. As a new composition of matter, the compound having the formula CH3 CH3 CHzCCH No references cited. 

1. AS A COMPOSITION OF MATTER, A COMPOUND FROM THE GROUP CONSISTING OF 